Foams And Articles Made From Foams Containing 1-Chloro-3,3,3-Trifluoropropene (HFCO-1233zd)

ABSTRACT

The present invention relates to poured-in place polyurethane foams and polyol premixes comprising 1-chloro-3,3,3-trifluoropropene (HFCO-1233zd) and one or more additional co-blowing agents.

CROSS REFERENCE TO RELATED APPLICATION

This application is a continuation of U.S. application Ser. No.14/679,802, filed Apr. 6, 2015, which application is a continuation ofU.S. patent application Ser. No. 13/191,070 filed Jul. 26, 2011, (nowU.S. Pat. No. 9,000,061, issued Apr. 7, 2015), which application claimsthe benefit of U.S. Provisional patent application Ser. No. 61/368,246filed Jul. 27, 2010, and U.S. Provisional patent application Ser. No.61/509,045, filed Jul. 18, 2011, the contents each of which areincorporated herein by reference in their entirety.

This application is also a continuation-in-part of U.S. patentapplication Ser. No. 12/847,381, filed on Jul. 30, 2010, (now U.S. Pat.No. 9,695,267, issued Jul. 4, 2017), which claims the benefit of U.S.Provisional patent application Ser. No. 61/232,836, filed Aug. 11, 2009,the contents each of which are incorporated herein by reference in theirentirety.

This application is also a continuation-in-part of U.S. patentapplication Ser. No. 12/276,137, filed Nov. 21, 2008, which claimspriority to U.S. Provisional patent application No. 60/989,977 filedNov. 25, 2007, and also is a continuation of PCT patent applicationnumber PCT/US07/64570 filed Mar. 21, 2007 and which is a continuation ofU.S. patent application Ser. No. 11/474,887 filed Jun. 26, 2006 andwhich claims priority to U.S. Provisional patent application Ser. No.60/784,731 filed Mar. 21, 2006, each of which is incorporated herein byreference in their entirety.

FIELD OF THE INVENTION

The present invention pertains to foams and to particular articles madeform foams and methods for the preparation thereof, and in particular topolyurethane and polyisocyanurate foams and methods for the preparationthereof.

BACKGROUND OF THE INVENTION

The class of foams known as low density, rigid to semi-rigidpolyurethane or polyisocyanurate foams has utility in a wide variety ofinsulation applications, including roofing systems, building panels,building envelope insulation, spray applied foams, one and two componentfroth foams, insulation for refrigerators and freezers, and so calledintegral skin foam for cushioning and safety application such assteering wheels and other automotive or aerospace cabin parts, shoesoles, and amusement park restraints. An important factor in thelarge-scale commercial success of many rigid to semi-rigid polyurethanefoams has been the ability of such foams to provide a good balance ofproperties. In general, rigid polyurethane and polyisocyanurate foamsshould provide outstanding thermal insulation, excellent fire resistanceproperties, and superior structural properties at reasonably lowdensities.

As is known, blowing agents are used to form the cellular structurerequired for such foams. It has been common to use liquid fluorocarbonblowing agents because of their ease of use, among other factors.Fluorocarbons not only act as blowing agents by virtue of theirvolatility, but also are encapsulated or entrained in the closed cellstructure of the rigid foam and are generally the major contributor tothe thermal conductivity properties of the rigid urethane foams. Afterthe foam is formed, the k-factor associated with the foam producedprovides a measure of the ability of the foam to resist the transfer ofheat through the foam material. As the k-factor decreases, this is anindication that the material is more resistant to heat transfer andtherefore a better foam for insulation purposes. Thus, materials thatproduce lower k-factor foams are generally desirable and advantageous.

In addition to the important performance characteristics mentionedabove, it has become increasingly important for the blowing agent(s)used in foamable compositions to have low global warming potential.

SUMMARY OF THE INVENTION

The present invention relates to the surprising and unexpected improvedproperties in rigid pour-in place polyurethane foam applications usingHFCO-1233zd (preferably the trans form thereof, HFCO-1233zd(E)) as theblowing agent. To this end, and in one aspect, the invention relates toa poured-in place polyurethane foam comprising: a polymeric foamstructure including a plurality of closed cells therein; andtrans-1-chloro-3,3,3-trifluoropropene (HFCO-1233zd(E)) contained in atleast a portion of said cells. Within the polymeric foam structure amajority of the cells contain a gas comprising said HFCO-1233zd(E). Incertain aspects, the gas is provided as at least 50% by volume of saidHFCO-1233zd(E). In further aspects, the gas within the cells consistsessentially of HFCO-1233zd(E).

In alternative aspects of the foregoing, the gas provided within thecell is provided as 1233zd (preferably 1233zd(E)) and at least oneadditional agent, which may be selected from any one or combination ofwater, organic acids that produce CO₂ and/or CO, hydrocarbons; ethers,halogenated ethers; esters, alcohols, aldehydes, ketones,pentafluorobutane; pentafluoropropane; hexafluoropropane;heptafluoropropane; trans-1,2 dichloroethylene; methylal, methylformate; 1-chloro-1,2,2,2-tetrafluoroethane (HCFC-124);1,1-dichloro-1-fluoroethane (HCFC-141b); 1,1,1,2-tetrafluoroethane(HFC-134a); 1,1,2,2-tetrafluoroethane (HFC-134); 1-chloro1,1-difluoroethane (HCFC-142b); 1,1,1,3,3-pentafluorobutane(HFC-365mfc); 1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea);trichlorofluoromethane (CFC-11); dichlorodifluoromethane (CFC-12);dichlorofluoromethane (HCFC-22); 1,1,1,3,3,3-hexafluoropropane(HFC-236fa); 1,1,1,2,3,3-hexafluoropropane (HFC-236e);1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea), difluoromethane (HFC-32);1,1-difluoroethane (HFC-152a); 1,1,1,3,3-pentafluoropropane (HFC-245fa);1,3,3,3-tetrafluoropropene (HFO-1234ze); 1,1,1,4,4,4-hexafluorobut-2-ene(HFO-1336mzzm); butane; isobutane; normal pentane; isopentane; orcyclopentane. In certain aspects, the additional agent is cyclopentane.In such embodiments, the gas component is comprised of from about 5 wt.% to about 99 wt. % of HFCO-1233zd(E) and from about 95 wt. % to about 1wt. % of cyclopentane; from about 25 wt. % to about 90 wt. % ofHFCO-1233zd(E) and from about 75 wt. % to about 10 wt. % ofcyclopentane; or from about 50 wt. % to about 85 wt. % of HFCO-1233zd(E)and from about 50 wt. % to about 15 wt. % of cyclopentane.

In further aspects the poured-in place polyurethane foam having1233zd(E) as the gas component has a free rise density of 1.87 lb/ft³and/or a core density of 2.21 lb/ft³. In even further aspects, thepoured-in place polyurethane foam having 1233zd(E) and cyclopentane asthe gas component has a free rise density of greater than 1.71 lb/ft³and/or a core density of greater than 2.33 lb/ft³.

In alternative embodiments, the present invention relates to a pour-inplace foam premix comprising a polyol; a blowing agent comprisingtrans-1-chloro-3,3,3-trifluoropropene (HFCO-1233zd(E)); at least onesurfactant; and at least one catalyst. In certain aspects, the pour-inplace foam premix has a foam reactivity gel time of about 55 secondsand/or a foam reactivity tack free time of about 100 seconds.

The blowing agent may further include one or more additional blowingagents, which may be selected from any one or combination of water,organic acids that produce CO₂ and/or CO, hydrocarbons; ethers,halogenated ethers; esters, alcohols, aldehydes, ketones,pentafluorobutane; pentafluoropropane; hexafluoropropane;heptafluoropropane; trans-1,2 dichloroethylene; methylal, methylformate; 1-chloro-1,2,2,2-tetrafluoroethane (HCFC-124);1,1-dichloro-1-fluoroethane (HCFC-141b); 1,1,1,2-tetrafluoroethane(HFC-134a); 1,1,2,2-tetrafluoroethane (HFC-134); 1-chloro1,1-difluoroethane (HCFC-142b); 1,1,1,3,3-pentafluorobutane(HFC-365mfc); 1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea);trichlorofluoromethane (CFC-11); dichlorodifluoromethane (CFC-12);dichlorofluoromethane (HCFC-22); 1,1,1,3,3,3-hexafluoropropane(HFC-236fa); 1,1,1,2,3,3-hexafluoropropane (HFC-236e);1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea); difluoromethane (HFC-32);1,1-difluoroethane (HFC-152a); 1,1,1,3,3-pentafluoropropane (HFC-245fa);1,3,3,3-tetrafluoropropene (HFO-1234ze); 1,1,1,4,4,4-hexafluorobut-2-ene(HFO-1336mzzm); butane; isobutane; normal pentane; isopentane; orcyclopentane. By way of a non-limiting example, in one embodiment, theadditional blowing agent is cyclopentane and the resulting premix has afoam reactivity gel time from 52 to 55 seconds and/or a foam reactivitytack free time from 85 to 100 seconds.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 shows the appearance of various polyol mixtures with HFC-245faafter having been aged at room temperature for 24 hours. From left toright, the polyols shown include: (1) Voranol 270, (2) Voranol 490, (3)Voranol 800, (4) Terate 4020, (5) Terate 2031, (6) Carpol GSP-280, (7)Multranol 3901.

FIG. 2 shows the appearance of various polyol mixtures with HFCO-1233zdafter having been aged at room temperature for 24 hours. From left toright, the polyols shown include: (1) Voranol 270, (2) Voranol 490, (3)Voranol 800, (4) Terate 4020, (5) Terate 2031, (6) Carpol GSP-280, (7)Multranol 3901.

FIG. 3 shows the comparative initial thermal conductivity of foamshaving HFC-245fa or HFCO-1233zd as blowing agents.

FIG. 4 shows the comparative thermal conductivity of foams havingHFC-245fa or HFCO-1233zd as blowing agents after 28 Days Aging atAmbient Temperature.

FIG. 5 shows the comparative initial thermal conductivity of foamshaving HFC-245fa, HFCO-1233zd (or HBA-2), cyclopentane, or HCFC-141b asblowing agents.

FIG. 6 shows the comparative thermal conductivity of foams havingHFC-245fa, HFCO-1233zd (or HBA-2), cyclopentane, or HCFC-141b as blowingagents after 28 Days Aging at Ambient Temperature.

FIG. 7 shows the comparative initial thermal conductivity of foamshaving varying component amounts of HFCO-1233zd (or HBA-2) andcyclopentane as blowing agent blends.

FIG. 8 shows the comparative thermal conductivity of foams havingvarying component amounts of HFCO-1233zd (or HBA-2) and cyclopentane asblowing agent blends, after 28 Days Aging at Ambient Temperature.

DESCRIPTION OF PREFERRED EMBODIMENTS

Applicants have come to recognize the existence of an unexpected andsurprising advantage when a certain hydrofluoroolefin, namelyHFCO-1233zd (preferably the trans form thereof, HFCO-1233zd(E)), is usedas the blowing agent in rigid polyurethane foam applications. Oneadvantage of the foams and the articles in accordance with certainpreferred embodiments is that the foams and articles are capable ofmaintaining superior thermal properties, including k-values, over anperiod of time that is unexpectedly and surprisingly long. As thoseskilled in the art will appreciate, this property provides a desirablecommercial advantage and value. Another advantage of the foams andarticles according to certain preferred embodiments of the presentinvention is that the foams and the articles formed therefrom havestrength advantages, including a desirable ratio of the strength of thefoam measured in the parallel direction to the strength of the foam inthe perpendicular direction.

Although applicants do not intend to be bound by or to any particulartheory of operation, it is believed that the exceptional physical andthermodynamic properties exhibited by the foams and articles of thepresent invention results, at least potentially in part, from the typeand nature of the cellular structure formed using the blowing agents ofthe present invention when used in combination with foldablecompositions comprising polyurethane adapted to the formation of rigidpolyurethane panels, and even more preferably poured in place apolyurethane panels.

As is known by those skilled in the art, polyurethane foam is usedextensively as the core insulation material in several types ofarticles, including metal panels in many applications, including thewalk-in cooler and freezer sectors. These foam core metal panels can bemanufactured by either continuous or discontinuous production methodsand both of such methods are adaptable for use within the scope of thepresent invention. In the construction industry, such articles in theform of rigid panels are employed as insulation in the building envelopeof commercial structures. In developed countries, the most commonly usedblowing agents for polyurethane foam in this application have prior tothis invention included HFC-245fa, HFC-134a and hydrocarbons. HCFC-141bis commonly used as the blowing agent in the majority of thepolyurethane foam markets in developing countries. As the low globalwarming potential initiative emerges in developed countries and the HCFCphase-out in developing countries approaches, there is an increasingworldwide need and desire for low global warming potential (LGWP)blowing agents.

Applicants expect that one advantage of the present invention is thatthe amount of HFCO-1233ZD, on a weight basis, need to for a particularrigid polyurethane foam formulation will be less than that for othercurrently used blowing agents, such as HFC-245fa. Applicants also expectthat the loss of blowing agent of the present invention from the polyolsystem, in particular during blending and during shipping in drums,should be decreased because applicants have recognized that the vaporpressure of HFCO-1233ZD is lower than that of HFC-245fa.

TABLE 1 Physical Properties of Blowing Agents Physical PropertiesHFCO-1233ZD HFC-245fa Cyclopentane HCFC-141b Formula — CF3CH2CF2H C5H10CH3CC12F Boiling Point, ° C./° F. >HFC-245fa 15.3/59.5 49.3/120.732.2/90.0 <HCFC-141b Liquid Density, g/cc @20° C./68° F. 1.30 1.32 0.741.24 Vapor Pressure, kPa @20° C./68° F. 106.3 122.0 34.0 69.0 VaporThermal Conductivity, 12.5¹ 12.5² 11 8.8 mW/mK @10° C.1/50° F.¹Honeywell measured value ²Property was measured at 24° C.

HFCO-1233ZD is a liquid blowing agent with low global warming potential.Table 2 summarizes the environmental properties of HFCO-1233ZD comparedto other commonly used blowing agents. Compared to HFC-245fa andHCFC-141b, HFCO-1233ZD has a significantly lower global warmingpotential. Furthermore, applicants test work indicates that HFCO-1233ZDwill not be considered a volatile organic compound (VOC) in the US andsubject to emission controls.

TABLE 2 Environmental Properties of Blowing Agents Environmental HFCO-HCFC- Properties 1233ZD HFC-245fa Cyclopentane 141b GWP (100 yr 7 103011 725 horizon, CO2 = 1)¹ Atmospheric 28 days 8.4 yrs Few Days 9.4 yrsLifetime VOC status No² No Yes No ¹HFC-245fa and HCFC-141b data wereobtained from IPCC report “Climate Change 2007 - The Physical ScienceBasis”. Cyclopentane data is a generally accepted value. ²Honeywell datashown that HFCO-1233ZD is not a VOC, pending EPA approval

Another advantage of the present invention is that HFCO-1233ZD isclassified as a non-flammable liquid blowing agent with neither a flashpoint nor vapor flame limits in air. Table 3 summarizes the flammabilityproperties of different blowing agents. HCFC-141b is classified ascombustible with vapor flame limits but no flash point whilehydrocarbons, such as cyclopentane, exhibit flash points and aretherefore flammable. The use of flammable materials will generallyrequire major capital investment in storage and processing equipmentmodifications.

TABLE 3 Flammability Properties of Blowing Agents Flammability HFCO-Properties 1233ZD HFC-245fa Cyclopentane HCFC-141b Vapor Flame Limits inAir Upper, Vol % None None 7.6 1.5 Lower, Vol % None None 17.7 8.7Flashpoint, None None −37.0/−34.6 None ° C./° F.

Furthermore, applicants recognize that toxicity assessments of newblowing agent molecules are vital before commercialization. The toxicityinformation directly affects the exposure guidelines during the foammanufacturing process. Furthermore, the information is critical toconsiderations in product stewardship and responsible care. Applicantshave found that HFCO-1233ZD has a very low order of acute toxicity whichis either equivalent to or better than that of HFC-245fa.

The use of HFCO-1233zd may be provided as a blowing agent in a polyolpremix, particularly premixes useful as a pour-in-place foam, and/or theprimary gas component of the resulting foam cell structure. HFCO-1233zdmay be provided alone or as a blend with one or more additional blowingagents. A nonexclusive list of such co-blowing agents include, but arenot limited to, water, organic acids that produce CO₂ and/or CO,hydrocarbons; ethers, halogenated ethers; esters, alcohols, aldehydes,ketones, pentafluorobutane; pentafluoropropane; hexafluoropropane;heptafluoropropane; trans-1,2 dichloroethylene; methylal, methylformate; 1-chloro-1,2,2,2-tetrafluoroethane (HCFC-124);1,1-dichloro-1-fluoroethane (HCFC-141b); 1,1,1,2-tetrafluoroethane(HFC-134a); 1,1,2,2-tetrafluoroethane (HFC-134); 1-chloro1,1-difluoroethane (HCFC-142b); 1,1,1,3,3-pentafluorobutane(HFC-365mfc); 1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea);trichlorofluoromethane (CFC-11); dichlorodifluoromethane (CFC-12);dichlorofluoromethane (HCFC-22); 1,1,1,3,3,3-hexafluoropropane(HFC-236fa); 1,1,1,2,3,3-hexafluoropropane (HFC-236e);1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea), difluoromethane (HFC-32);1,1-difluoroethane (HFC-152a); 1,1,1,3,3-pentafluoropropane (HFC-245fa);1,3,3,3-tetrafluoropropene (HFO-1234ze—including its trans or “E”isomer); 1,1,1,4,4,4-hexafluorobut-2-ene (HFO-1336mzzm—including its cisor “Z” isomer); butane; isobutane; normal pentane; isopentane;cyclopentane, or combinations thereof. In certain aspects, particularlyin the pour-in-place context, the co-blowing agent is a cyclopentane

The blowing agent component is usually present in the polyol premixcomposition in an amount of from about 1 wt. % to about 30 wt. %,preferably from about 3 wt. % to about 25 wt. %, and more preferablyfrom about 5 wt. % to about 25 wt. %, by weight of the polyol premixcomposition. When both 1233zd and one or more additional blowing agentsare present, 1233zd may be present in the blowing agent component in anamount of from about 5 wt. % to about 99 wt. %, from about 10 wt. % toabout 90 wt. %, or from about 25 wt. % to about 85 wt. %, by weight ofthe blowing agent component; and the optional blowing agent is usuallypresent in the blowing agent component in an amount of from about 95 wt.% to about 1 wt. %, from about 90 wt. % to about 10 wt. %, or from about15 wt. % to about 75 wt. %, by weight of the blowing agent component.When 1233zd is provided in a blend with cyclopentane, 1233zd may bepresent in the blowing agent component in an amount of from about 5 wt.% to about 99 wt. %, from about 25 wt. % to about 90 wt. %, or fromabout 50 wt. % to about 85 wt. %, by weight of the blowing agentcomponent; and cyclopentane is usually present in the blowing agentcomponent in an amount of from about 95 wt. % to about 1 wt. %, fromabout 75 wt. % to about 10 wt. %, or from about 50 wt. % to about 15 wt.%, by weight of the blowing agent component

The polyol component, which may include mixtures of polyols, can be anypolyol which reacts in a known fashion with an isocyanate in preparing apolyurethane or polyisocyanurate foam. Useful polyols comprise one ormore of a sucrose containing polyol; phenol, a phenol formaldehydecontaining polyol; a glucose containing polyol; a sorbitol containingpolyol; a methylglucoside containing polyol; an aromatic polyesterpolyol; glycerol; ethylene glycol; diethylene glycol; propylene glycol;graft copolymers of polyether polyols with a vinyl polymer; a copolymerof a polyether polyol with a polyurea; one or more of (a) condensed withone or more of (b): (a) glycerine, ethylene glycol, diethylene glycol,trimethylolpropane, ethylene diamine, pentaerythritol, soy oil,lecithin, tall oil, palm oil, castor oil; (b) ethylene oxide, propyleneoxide, a mixture of ethylene oxide and propylene oxide; or combinationsthereof. The polyol component is preferably present in the polyol premixcomposition in an amount of from about 60 wt. % to about 95 wt. %,preferably from about 65 wt. % to about 95 wt. %, and more preferablyfrom about 70 wt. % to about 90 wt. %, by weight of the polyol premixcomposition.

In certain embodiments, the polyol premix composition may also containat least one silicone-containing surfactant. The silicone-containingsurfactant is used to aid in the formation of foam from the mixture, aswell as to control the size of the bubbles of the foam so that a foam ofa desired cell structure is obtained. Preferably, a foam with smallbubbles or cells therein of uniform size is desired since it has themost desirable physical properties such as compressive strength andthermal conductivity. Also, it is critical to have a foam with stablecells which do not collapse prior to forming or during foam rise.

Silicone surfactants for use in the preparation of polyurethane orpolyisocyanurate foams are available under a number of trade names knownto those skilled in this art. Such materials have been found to beapplicable over a wide range of formulations allowing uniform cellformation and maximum gas entrapment to achieve very low density foamstructures. The preferred silicone surfactant comprises a polysiloxanepolyoxyalkylene block co-polymer. Some representative siliconesurfactants useful for this invention are Momentive's L-5130, L-5180,L-5340, L-5440, L-6100, L-6900, L-6980 and L-6988; Air Products DC-193,DC-197, DC-5582, and DC-5598; and B-8404, B-8407, B-8409 and B-8462 fromGoldschmidt AG of Essen, Germany. Others are disclosed in U.S. Pat. Nos.2,834,748; 2,917,480; 2,846,458 and 4,147,847. The silicone surfactantcomponent is usually present in the polyol premix composition in anamount of from about 0.5 wt. % to about 5.0 wt. %, preferably from about1.0 wt. % to about 4.0 wt. %, and more preferably from about 1.5 wt. %to about 3.0 wt. %, by weight of the polyol premix composition.

The polyol premix composition may optionally contain a non-siliconesurfactant, such as a non-silicone, non-ionic surfactant. Such mayinclude oxyethylated alkylphenols, oxyethylated fatty alcohols, paraffinoils, castor oil esters, ricinoleic acid esters, turkey red oil,groundnut oil, paraffins, and fatty alcohols. A preferred non-siliconenon-ionic surfactant is LK-443 which is commercially available from AirProducts Corporation. When a non-silicone, non-ionic surfactant used, itis usually present in the polyol premix composition in an amount of fromabout 0.25 wt. % to about 3.0 wt. %, preferably from about 0.5 wt. % toabout 2.5 wt. %, and more preferably from about 0.75 wt. % to about 2.0wt. %, by weight of the polyol premix composition.

The polyol premix composition may also include one or more catalysts, inparticular amine catalysts, such as, but not limited to, primary amine,secondary amine or tertiary amine. Useful tertiary amine catalystsnon-exclusively include N,N,N′,N″,N″-pentamethyldiethyltriamine,N,N-dicyclohexylmethylamine; N,N-ethyldiisopropylamine;N,N-dimethylcyclohexylamine; N,N-dimethylisopropylamine;N-methyl-N-isopropylbenzylamine; N-methyl-N-cyclopentylbenzylamine;N-isopropyl-N-sec-butyl-trifluoroethylamine;N,N-diethyl-(α-phenylethyl)amine, N,N,N-tri-n-propylamine, orcombinations thereof. Useful secondary amine catalysts non-exclusivelyinclude dicyclohexylamine; t-butylisopropylamine; di-t-butylamine;cyclohexyl-t-butylamine; di-sec-butylamine, dicyclopentylamine;di-(α-trifluoromethylethyl)amine; di-(α-phenylethyl)amine; orcombinations thereof. Useful primary amine catalysts non-exclusivelyinclude: triphenylmethylamine and 1,1-diethyl-n-propylamine.

Other useful amines includes morpholines, imidazoles, ether containingcompounds, and the like. These include

-   dimorpholinodiethylether-   N-ethylmorpholine-   N-methylmorpholine-   bis(dimethylaminoethyl) ether-   imidizole-   n-methylimidazole-   1,2-dimethylimidazole-   dimorpholinodimethylether-   N,N,N′,N′,N″,N″-pentamethyldiethylenetriamine-   N,N,N′,N′,N″,N″-pentaethyldiethylenetriamine-   N,N,N′,N′,N″,N″-pentamethyldipropylenetriamine-   bis(diethylaminoethyl) ether-   bis(dimethylaminopropyl) ether.

The preparation of polyurethane or polyisocyanurate foams using thecompositions described herein may follow any of the methods well knownin the art can be employed, see Saunders and Frisch, Volumes I and IIPolyurethanes Chemistry and technology, 1962, John Wiley and Sons, NewYork, N.Y. or Gum, Reese, Ulrich, Reaction Polymers, 1992, OxfordUniversity Press, New York, N.Y. or Klempner and Sendijarevic, PolymericFoams and Foam Technology, 2004, Hanser Gardner Publications,Cincinnati, Ohio. In general, polyurethane or polyisocyanurate foams areprepared by combining an isocyanate, the polyol premix composition, andother materials such as optional flame retardants, colorants, or otheradditives. These foams can be rigid, flexible, or semi-rigid, and canhave a closed cell structure, an open cell structure or a mixture ofopen and closed cells.

It is convenient in many applications to provide the components forpolyurethane or polyisocyanurate foams in pre-blended formulations. Mosttypically, the foam formulation is pre-blended into two components. Theisocyanate and optionally other isocyanate compatible raw materials,including but not limited to blowing agents and certain siliconesurfactants, comprise the first component, commonly referred to as the“A” component. The polyol mixture composition, including surfactant,catalysts, blowing agents, and optional other ingredients comprise thesecond component, commonly referred to as the “B” component. In anygiven application, the “B” component may not contain all the abovelisted components, for example some formulations omit the flameretardant if flame retardancy is not a required foam property.Accordingly, polyurethane or polyisocyanurate foams are readily preparedby bringing together the A and B side components either by hand mix forsmall preparations and, preferably, machine mix techniques to formblocks, slabs, laminates, pour-in-place panels and other items, sprayapplied foams, froths, and the like. Optionally, other ingredients suchas fire retardants, colorants, auxiliary blowing agents, water, and evenother polyols can be added as a stream to the mix head or reaction site.Most conveniently, however, they are all, with the exception of water,incorporated into one B component as described above.

A foamable composition suitable for forming a polyurethane orpolyisocyanurate foam may be formed by reacting an organicpolyisocyanate and the polyol premix composition described above. Anyorganic polyisocyanate can be employed in polyurethane orpolyisocyanurate foam synthesis inclusive of aliphatic and aromaticpolyisocyanates. Suitable organic polyisocyanates include aliphatic,cycloaliphatic, araliphatic, aromatic, and heterocyclic isocyanateswhich are well known in the field of polyurethane chemistry. These aredescribed in, for example, U.S. Pat. Nos. 4,868,224; 3,401,190;3,454,606; 3,277,138; 3,492,330; 3,001,973; 3,394,164; 3,124.605; and3,201,372. Preferred as a class are the aromatic polyisocyanates.

Representative organic polyisocyanates correspond to the formula:

R(NCO)_(z)

wherein R is a polyvalent organic radical which is either aliphatic,aralkyl, aromatic or mixtures thereof, and z is an integer whichcorresponds to the valence of R and is at least two. Representative ofthe organic polyisocyanates contemplated herein includes, for example,the aromatic diisocyanates such as 2,4-toluene diisocyanate, 2,6-toluenediisocyanate, mixtures of 2,4- and 2,6-toluene diisocyanate, crudetoluene diisocyanate, methylene diphenyl diisocyanate, crude methylenediphenyl diisocyanate and the like; the aromatic triisocyanates such as4,4′,4″-triphenylmethane triisocyanate, 2,4,6-toluene triisocyanates;the aromatic tetraisocyanates such as4,4′-dimethyldiphenylmethane-2,2′5,5-′tetraisocyanate, and the like;arylalkyl polyisocyanates such as xylylene diisocyanate; aliphaticpolyisocyanate such as hexamethylene-1,6-diisocyanate, lysinediisocyanate methylester and the like; and mixtures thereof. Otherorganic polyisocyanates include polymethylene polyphenylisocyanate,hydrogenated methylene diphenylisocyanate, m-phenylene diisocyanate,naphthylene-1,5-diisocyanate, 1-methoxyphenylene-2,4-diisocyanate,4,4′-biphenylene diisocyanate, 3,3′-dimethoxy-4,4′-biphenyldiisocyanate, 3,3′-dimethyl-4,4′-biphenyl diisocyanate, and3,3′-dimethyldiphenylmethane-4,4′-diisocyanate; Typical aliphaticpolyisocyanates are alkylene diisocyanates such as trimethylenediisocyanate, tetramethylene diisocyanate, and hexamethylenediisocyanate, isophorene diisocyanate, 4,4′-methylenebis(cyclohexylisocyanate), and the like; typical aromatic polyisocyanates include m-,and p-phenylene disocyanate, polymethylene polyphenyl isocyanate, 2,4-and 2,6-toluenediisocyanate, dianisidine diisocyanate, bitoyleneisocyanate, naphthylene 1,4-diisocyanate,bis(4-isocyanatophenyl)methene, bis(2-methyl-4-isocyanatophenyl)methane,and the like. Preferred polyisocyanates are the polymethylene polyphenylisocyanates. Particularly the mixtures containing from about 30 to about85 percent by weight of methylenebis(phenyl isocyanate) with theremainder of the mixture comprising the polymethylene polyphenylpolyisocyanates of functionality higher than 2. These polyisocyanatesare prepared by conventional methods known in the art. In the presentinvention, the polyisocyanate and the polyol are employed in amountswhich will yield an NCO/OH stoichiometric ratio in a range of from about0.9 to about 5.0. In the present invention, the NCO/OH equivalent ratiois, preferably, about 1.0 or more and about 3.0 or less, with the idealrange being from about 1.1 to about 2.5. Especially suitable organicpolyisocyanate include polymethylene polyphenyl isocyanate,methylenebis(phenyl isocyanate), toluene diisocyanates, or combinationsthereof.

In the preparation of polyisocyanurate foams, trimerization catalystsare used for the purpose of converting the blends in conjunction withexcess A component to polyisocyanurate-polyurethane foams. Thetrimerization catalysts employed can be any catalyst known to oneskilled in the art, including, but not limited to, glycine salts,tertiary amine trimerization catalysts, quaternary ammoniumcarboxylates, and alkali metal carboxylic acid salts and mixtures of thevarious types of catalysts. Preferred species within the classes arepotassium acetate, potassium octoate, andN-(2-hydroxy-5-nonylphenol)methyl-N-methylglycinate.

Conventional flame retardants can also be incorporated, preferably inamount of not more than about 20 percent by weight of the reactants.Optional flame retardants include tris(2-chloroethyl)phosphate,tris(2-chloropropyl)phosphate, tris(2,3-dibromopropyl)phosphate,tris(1,3-dichloropropyl)phosphate, tri(2-chloroisopropyl)phosphate,tricresyl phosphate, tri(2,2-dichloroisopropyl)phosphate, diethylN,N-bis(2-hydroxyethyl) aminomethylphosphonate, dimethylmethylphosphonate, tri(2,3-dibromopropyl)phosphate,tri(1,3-dichloropropyl)phosphate, and tetra-kis-(2-chloroethyl)ethylenediphosphate, triethylphosphate, diammonium phosphate, varioushalogenated aromatic compounds, antimony oxide, aluminum trihydrate,polyvinyl chloride, melamine, and the like. Other optional ingredientscan include from 0 to about 7 percent water, which chemically reactswith the isocyanate to produce carbon dioxide. This carbon dioxide actsas an auxiliary blowing agent. In the case of this invention, the watercannot be added to the polyol blend but, if used, can be added as aseparate chemical stream. Formic acid is also used to produce carbondioxide by reacting with the isocyanate and is optionally added to the“B” component.

In addition to the previously described ingredients, other ingredientssuch as, dyes, fillers, pigments and the like can be included in thepreparation of the foams. Dispersing agents and cell stabilizers can beincorporated into the present blends. Conventional fillers for useherein include, for example, aluminum silicate, calcium silicate,magnesium silicate, calcium carbonate, barium sulfate, calcium sulfate,glass fibers, carbon black and silica. The filler, if used, is normallypresent in an amount by weight ranging from about 5 parts to 100 partsper 100 parts of polyol. A pigment which can be used herein can be anyconventional pigment such as titanium dioxide, zinc oxide, iron oxide,antimony oxide, chrome green, chrome yellow, iron blue siennas,molybdate oranges and organic pigments such as para reds, benzidineyellow, toluidine red, toners and phthalocyanines.

The polyurethane or polyisocyanurate foams produced can vary in densityfrom about 0.5 pounds per cubic foot to about 60 pounds per cubic foot,preferably from about 1.0 to 20.0 pounds per cubic foot, and mostpreferably from about 1.5 to 6.0 pounds per cubic foot. The densityobtained is a function of how much of the blowing agent or blowing agentmixture disclosed in this invention plus the amount of auxiliary blowingagent, such as water or other co-blowing agents is present in the Aand/or B components, or alternatively added at the time the foam isprepared. These foams can be rigid, flexible, or semi-rigid foams, andcan have a closed cell structure, an open cell structure or a mixture ofopen and closed cells. These foams are used in a variety of well knownapplications, including but not limited to thermal insulation,cushioning, flotation, packaging, adhesives, void filling, crafts anddecorative, and shock absorption.

The following non-limiting examples serve to illustrate the invention.

EXAMPLES Comparative Example 1

In the panel foam industry, it is often necessary to blend a blowingagent into the polyol premix in the manufacturing facility regardless ofthe production methods, either continuous or discontinuous. Adequatemiscibility of blowing agent in polyol is necessary to producepolyurethane foam, and in particular rigid polyurethane foam panels,with desirable physical and thermal properties. The miscibility ofHFCO-1233ZD was compared to HFC-245fa in various polyols commonly usedin panel foam applications. Table 4 lists the name, type and suppliersof polyols evaluated in this miscibility study.

In this experiment, a mixture of 40 wt % blowing agent and 60 wt %polyol was prepared in a Fischer Porter tube. The tube was thenvigorously shaken and thoroughly mixed. The appearance of the mixturewas recorded after the tubes were conditioned at room temperature for 24hours. If a phase separation was detected, the amount of blowing agentdissolved was indirectly calculated by measuring the height of theblowing agent phase which had settled at the bottom of the tube. Table 5shows the miscibility of HFCO-1233ZD and HFC-245fa in the evaluatedpolyols correspondingly. Furthermore, FIG. 1 and FIG. 2 show theappearance of the polyol mixture with blowing agent after having beenaged at room temperature for 24 hours.

Both HFCO-1233ZD and HFC-245fa appear to be more miscible in thepolyether polyols than in the polyester polyols evaluated. At least 40wt % of either blowing agent can be blended into the polyether polyolsevaluated without phase separation. Furthermore, the miscibility of bothblowing agents in polyester polyol is considered typical. All in all,HFCO-1233ZD has demonstrated excellent solubility in polyether polyolsevaluated and adequate miscibility in polyester polyols tested.

TABLE 4 Polyols Evaluated in the Miscibility Study Polyol Name PolyolType Suppliers 1 Voranol ® 270 Glycerine Initiated Dow ChemicalPolyether Polyol 2 Voranol ® 490 Surcose/Glycerine Dow ChemicalInitiated Polyether Polyol 3 Voranol ® 800 Aliphatic-amine initiated DowChemical Polyether Polyol 4 Terate ® 4020 Aromatic Polyester InvistaPolyol 5 Terate ® 2031 Aromatic Polyester Invista Polyol 6 Carpol ®GSP-280 Surcose/Glycerine Carpenter Initiated Polyether Polyol 7Multranol ® 3901 Polyether Polyol Bayer

TABLE 5 Miscibility of HFC-245fa and HFCO-1233ZD in Various PolyolsHFCO-1233ZD HFC-245fa Phase Wt % Phase Wt % Polyol Name SeparationMiscibility Separation Miscibility Voranol ® 270 No ≧40 No ≧40 Voranol ®490 No ≧40 No ≧40 Voranol ® 800 No ≧40 No ≧40 Terate ® 4020 Yes ~20 Yes~18 Terate ® 2031 Yes ~11 Yes ~20 Carpol ® GSP-280 No ≧40 No ≧40Multranol ® 3901 No ≧40 No ≧40

Comparative Example 2

Foam core metal panels are used extensively in many differentapplications, such as walk-in coolers, walk-in freezer, cold storage andvarious commercial structures. One of the key performance criteria formetal panels is the R-value, i.e. the reciprocal of thermalconductivity. Therefore, the focus of this study was to compare thethermal conductivity of foams with either HFC-245fa or HFCO-1233ZD. Thephysical properties, such as foam reactivity, dimensional stability andcompressive strength, were also compared.

The compositions of the formulation with different blowing agents arelisted in Table 6. The panel foam formulation utilized was developed toyield a free rise density of about 1.9 lb/ft3. Using 20% overpacking,the resultant density of the foams was between 2.2 lb/ft3 and 2.3lb/ft3. All the discontinuous panel foams were prepared by utilizing theEdge-Sweets high pressure foam machine with processing conditions givenin Table 7. The foam was shot into a preheated mold, at 120° F. to 125°F., and allowed to cure in a 130° F. oven for 20 minutes beforedemolding. All physical property and thermal conductivity testing, wasperformed at least 24 hours after the foam was prepared.

One advantage of the present compositions, foams and articles is that inpreferred embodiments the present blowing agents may be considered as a“drop-in” replacement for formulations currently using HFC-124fa in suchapplications. The discontinuous panel foam formulation used wasdeveloped for HFC-245fa as the blowing agent.

TABLE 6 Formulation of Discontinuous Panel Foam Evaluated ComponentsHFCO-1233ZD HFC-245fa Polyether Polyol 65.0 65.0 Polyester Polyol 35.035.0 Catalyst 2.0 2.0 Surfactant 1.5 1.5 Flame Retardant 22.0 22.0 Water2.0 2.0 Blowing Agent Equal-molar 24.0 Isocyanate, Index = 110 143.6143.6

TABLE 7 Discontinuous Panel Foams' Preparation Parameters and ConditionsParameters Conditions Equipment Edge-Sweets High Pressure MachineMachine Pressure 2000 psi/13.8 MPa Foam Output Flow Output 15 lb/min/6.8kg/min Polyol Temperature 68-72° F./20-22° C. Isocyanate Temperature68-72° F./20-22° C. Injection Time, blowing 3.0-3.1 seconds agentdependent Mold Temperature 120° F.-125° F./48.9° C.-51.7° C. MoldDimensions 2′ × 1′ × 2″/30.5 cm × 15.3 cm × 5.1 cm

TABLE 8 Resultant Foam Density of Discontinuous Panel Foams Foam DensityHFCO-1233ZD HFC-245fa Free Rise Density, lb/ft3 1.87 1.86 Free RiseDensity, kg/m3 30.0 29.8 Core Density, lb/ft3 2.21 2.23 Core Density,kg/m3 35.2 35.2

The free rise density and core density of the discontinuous panel foamsprepared are tabulated in Table 8. The resultant free rise and core foamdensities are within 5% range of each other with HFCO-1233ZD andHFC-245fa as blowing agents. The comparison of physical properties, suchas foam reactivity, dimensional stability and compressive strength, andthermal conductivity determined are relevant and valid for evaluationpurposes.

The thermal conductivity of the foams were evaluated at five meantemperatures, 20° F./−7° C., 40° F./4° C., 55° F./13° C., 70° F./21° C.and 110° F./43° C. FIG. 3 and FIG. 4 show the initial and 28-day agedthermal conductivity of the foams respectively. The foams containingHFCO-1233ZD provides better thermal insulation value, approximately 5%lower initial thermal conductivity, than those with HFC-245fa at allevaluated temperatures. The difference in thermal conductivity increasedto 10% after the foams were aged for 28 days. Compared to foam withHFC-245fa, those with HFCO-1233ZD may provide either similar thermalinsulation value with thinner foam insulation or offer better energyefficiency at an equal foam thickness.

Comparative Example 3

Polyurethane foams with HFCO-1233ZD blowing agent provide comparablephysical properties compared to those foams with HFC-245fa. Table 9shows the foam reactivity, dimensional stability and compressivestrength of both systems. Comparable foam reactivity and dimensionalstability were found for both foams. Comparing the parallel andperpendicular compressive strength, the data show surprisingly andunexpectedly that that rigid polyurethane foam, especially poured-inplace foam panels, with HFCO-1233ZD exhibits an advantageously greaterisotropic cell structure than that with HFC-245fa.

TABLE 9 Foam Reactivity and Typical Properties HFCO-1233ZD HFC-245faFoam Reactivity Gel Time, sec 38 40 Tack Free Time, sec 150 127Dimensional Stability, Vol. % Change¹ Cold, −29° C., Aged 28 Days −0.69−0.17 Hot, 90° C., Aged 28 Days 2.60 4.18 Hot & Humid, 70° C./95% RH,8.21 6.66 Aged 28 Days Compressive Strength² Perpendicular, psi 17.320.8 Perpendicular, kPa 119.3 143.4 Parallel, psi 18.6 24.5 Parallel,kPa 128.2 168.9 ¹Dimensional stability of foam was evaluated as per ASTMD-2126-04 ²Compressive strength of foam was evaluated as per ASTM D-1621

Comparative Example 4

The thermal conductivity, i.e. the reciprocal of R-value, reactivity,dimensional stability, compressive strength and flammability ofpolyurethane foams with HFCO-1233zd(E) were compared against those thirdgeneration liquid blowing agents, such as 245fa and cyclopentane, andsecond generation liquid blowing agent, 141b. Furthermore, properties offoams with various compositions of HFCO-1233zd(E)/cyclopentane blendswere also evaluated aiming to seek a balance between superior foamproperties and desired cost.

The compositions of a generic formulation with various blowing agentsare listed in Table 10. This generic polyurethane foam formulationutilized was developed to yield a free rise density of about 1.9 lb/ft³.With approximately 20% overpacking, the density of the prepared foamsranged from 2.2 lb/ft³ to 2.3 lb/ft³. All the foams were prepared by ahand-mixing method with processing conditions given in Table 11. Theblended foam was poured into a mold at 104° F. and allowed to cure for30 minutes before demolding. All physical property and thermalconductivity testing was performed at least 24 hours after the foam wasprepared. This experiment is considered as a “drop-in” replacement studyto determine the blowing agent feasibility. The generic polyurethanefoam formulation used in this study was developed using 245fa as blowingagent. The formulation used in this evaluation for other blowing agentsis not necessarily optimal.

TABLE 10 Generic Formulation of Discontinuous Panel Foam EvaluatedComponents HBA-2 245fa Cyclopentane 141b Polyether Polyol 65.0 65.0 65.065.0 Polyester Polyol 35.0 35.0 35.0 35.0 Catalysts 2.0 2.0 2.0 2.0Surfactant 1.5 1.5 1.5 1.5 Flame Retardant 22.0 22.0 22.0 22.0 Water 2.02.0 2.0 2.0 Blowing Agent Equal-Molar 24.0 12.5 20.9 Isocyanate, Index =110 143.6 143.6 143.6 143.6

TABLE 11 Hand-Mixing Method - Preparation Parameters and ConditionsParameters Conditions Component Temperature Polyol Premix 68° F./20° C.Isocyanate 68° F./20° C. Stirring Speed 5000 RPM Duration 5 seconds MoldDimensions 4″ × 12″ × 12″/10 cm × 30 cm × 30 cm Mold Temperature 104°F./40° C. 

TABLE 12A Densities of Foams with Various Blowing Agents PhysicalProperties HBA-2 245fa Cyclopentane 141b Free Rise Density, lb/ft³ 1.831.77 1.85 1.92 Free Rise Density, kg/m³ 29.3 28.3 29.7 29.8 CoreDensity, lb/ft³ 2.35 2.29 2.31 2.32 Core Density, kg/m³ 37.6 36.7 37.137.2

TABLE 12B HBA-2/Cyclopentane mol % Ratio Physical Properties 100/0 75/2550/50 25/75 0/100 Free Rise Density, lb/ft³ 1.83 1.83 1.79 1.71 1.85Free Rise Density, kg/m³ 29.3 29.3 28.6 27.3 29.7 Core Density, lb/ft³2.35 2.33 2.33 2.37 2.35 Core Density, kg/m³ 37.6 37.4 37.4 38.0 37.7

When compared the free rise density and core density of the polyurethanefoams prepared with blowing agents or blowing agent blends, they arewithin 10% range of each other in Tables 12A and 12B. Since the foamsshare essentially identical density, comparisons of their physical,thermal properties are considered as fair and valid.

TABLE 13 Reactivity and Properties of Foams with Various Blowing AgentsHBA-2 245fa Cyclopentane 141b Foam Reactivity Gel Time, sec 55 55 52 52Tack Free Time, sec 100 100 95 95 Dimensional Stability, ΔVol %¹ −29°C., Aged 28 Days −1.21 −1.75 −1.13 −1.61 90° C., Aged 28 Days 3.14 3.867.67 9.62 70° C./95% RH, 3.83 3.98 6.42 14.96 Aged 28 Days CompressiveStrength² Parallel, psi 40.2 41.3 36.2 38.9 Parallel, kPa 277.5 284.5249.9 268.0 Perpendicular, psi 27.2 28.8 24.0 27.7 Perpendicular, kPa187.5 198.5 165.2 190.7 ¹Dimensional stability of foam was evaluated asper ASTM D-2126-04 ²Compressive strength of foam was evaluated as perASTM D-1621

According to the results in Table 13, foams with HBA-2 demonstratereactivity physical properties comparable to those with 245fa.Furthermore, they demonstrate significantly better dimensional stabilityat high temperatures than those with cyclopentane or 141b, andsignificantly higher compressive strength that those with cyclopentane.

TABLE 14 Foam Reactivity and Properties with Various Blowing AgentsBlends HBA-2/Cyclopentane mol % Ratio 100/0 75/25 50/50 25/75 0/100Physical Properties Gel Time, sec 55 54 53 52 52 Tack Free Time, sec 10099 95 85 100 Dimensional Stability, ΔVol %¹ −29° C., Aged −1.21 −1.15−1.53 −2.15 −1.13 28 Days 90° C., Aged 28 Days 3.14 4.66 5.03 3.44 7.6770° C./95% RH, 3.83 3.40 5.93 5.58 6.42 Aged 28 Days CompressiveStrength² Parallel, psi 40.2 40.0 35.0 35.8 36.2 Parallel, kPa 277.5275.8 241.6 247.0 249.9 Perpendicular, psi 27.2 26.1 24.9 28.4 24.0Perpendicular, kPa 187.5 180.0 171.4 195.8 165.2 ¹Dimensional stabilityof foam was evaluated as per ASTM D-2126-04 ²Compressive strength offoam was evaluated as per ASTM D-1621

Referring to Table 14, blending 1233zd (HBA-2) with cyclopentane appearsto enhance various physical properties when compared to foams with onlycyclopentane. For instance, at high temperature conditions, such as 90°C. and 70° C./95% RH, the dimensional stability is improved as theconcentration of HBA-2 increased in the blend. Also, it is important tostress that foams with 75/25 mol % HBA-2/cyclopentane provides almostidentical foam reactivity and similar superior physical properties tofoams blown with HBA-2 alone. However, mixtures of cyclopentane andHBA-2 are considered as flammable which probably require explosion-proofequipment for processing.

FIG. 5 and FIG. 6 show the initial and 28-day aged thermal conductivityof foams with various blowing agents respectively. Foams containingHBA-2 provide better thermal insulation value, approximately 4% lowerinitial thermal conductivity, than those with 245fa at all evaluatedtemperatures, 40° F./4° C., 55° F./13° C., 70° F./21° C. and 110° F./43°C. A similar phenomenon was also noted after 28 days aging at roomtemperature but with a wider discrepancy, about 6% between those curves.In other words, foams with HBA-2 retained its thermal insulation valuebetter than their counterparts with HBA-2. Although foams with 141bappear to have better thermal insulation value than those with HBA-2 athigher temperatures, the trend begins to show a reverse behavior attemperatures approximately 45° F./7° C. and lower, which falls into theoperating temperature range of pour-in-place applications, such aswalk-in freezers and cold storage. Furthermore, after 28 days of aging,foams with HBA-2 demonstrate considerably better thermal insulationvalue than all blowing agents, including, 141b, at all evaluatedtemperatures. The thermal conductivity of foams with cyclopentane is thehighest among all tested samples regardless of evaluated temperaturesand aging durations. Furthermore, the thermal conductivity of foams withcyclopentane begins to level off when the evaluated temperatures arebelow approximately 75° F., reducing its effectiveness in cold storageapplications, such as coolers and freezers that require foams withsuperior thermal insulation value at 20° F. and 55° F. correspondingly.

According to FIG. 7, although the thermal insulation value of foamsdeteriorates as the percentage of cyclopentane in the blend increases,the trend does not appear to be linear. Blending of up to 50 mol % ofcyclopentane with HBA-2 demonstrates no significant impact on initialthermal conductivity throughout the temperatures evaluated. This isparticularly beneficial to pour-in-place applications which are lookingfor foam with a balance of superior thermal properties and acceptablecost of blowing agent.

As illustrated in FIG. 8, the aged thermal conductivity of foams with acomposition equal to or higher than 75 mol % cyclopentane appears tohave a more noticeable plateau effect than the others. This phenomenonmay not be favorable to cold chain application due to its low operationtemperatures. Although certain HBA-2/cyclopentane blends may be able toprovide a desired balance between properties and cost, foams with HBA-2are still the best with respect to both initial and aged thermalinsulation values. Also note that the HBA-2 foams retain their k-factorbetter than any of the blends evaluated.

TABLE 15A Measured Flame Height of Foam Samples During the FlammabilityTest B2 Test Evaluation¹ HBA-2 245fa 141b Cyclopentane Flame Height, cm10.0 12.0 12.0 15.0 ¹Flammability of foams was evaluated as per DIN4102-1: Class B2 Materials

TABLE 15B Measured Flame Height of Foam Samples During the FlammabilityTest HBA-2/Cyclopentane mol % Ratio B2 Test Evaluation¹ 100/0 75/2550/50 25/75 0/100 Flame Height, cm 10.0 11.0 12.0 13.0 15.0¹Flammability of foams was evaluated as per DIN 4102-1: Class B2Materials

All foams were evaluated for flammability performance using the DIN 4102B2 test method. In order to pass the DIN 4102-1: Class B2 materialevaluation, the flame height could not surpass the gauge which located15 cm above the ignition point during the first 15 seconds of the test.According to Table 15A and 15B, Foams with HBA-2 has the best flameretardancy when compared to those with 245fa, 141b or cyclopentane.Foams with cyclopentane only passed the evaluation marginally. For theblends, as the concentration of cyclopentane increases, the flameretardancy decreases.

What is claimed is:
 1. A poured-in place polyurethane foam comprising: apolymeric foam structure including a plurality of closed cells therein;and trans-1-chloro-3,3,3-trifluoropropene (HFCO-1233zd(E)) contained inat least a portion of said cells.
 2. The poured-in place polyurethanefoam of claim 1 wherein a majority of said cells contain a gascomprising said HFCO-1233zd(E).
 3. The poured-in place polyurethane foamof claim 2 wherein said gas comprises at least 50% by volume of saidHFCO-1233zd(E).
 4. The poured-in place polyurethane foam of claim 2wherein said gas consists essentially of HFCO-1233zd(E).
 5. Thepoured-in place polyurethane foam of claim 1 where said cells contain agas comprising HFCO-1233zd(E) and at least one additional agent selectedfrom the group consisting of water, organic acids that produce CO₂and/or CO, hydrocarbons; ethers, halogenated ethers; esters, alcohols,aldehydes, ketones, pentafluorobutane; pentafluoropropane;hexafluoropropane; heptafluoropropane; trans-1,2 dichloroethylene;methylal, methyl formate; 1-chloro-1,2,2,2-tetrafluoroethane (HCFC-124);1,1-dichloro-1-fluoroethane (HCFC-141b); 1,1,1,2-tetrafluoroethane(HFC-134a); 1,1,2,2-tetrafluoroethane (HFC-134); 1-chloro1,1-difluoroethane (HCFC-142b); 1,1,1,3,3-pentafluorobutane(HFC-365mfc); 1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea);trichlorofluoromethane (CFC-11); dichlorodifluoromethane (CFC-12);dichlorofluoromethane (HCFC-22); 1,1,1,3,3,3-hexafluoropropane(HFC-236fa); 1,1,1,2,3,3-hexafluoropropane (HFC-236e);1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea), difluoromethane (HFC-32);1,1-difluoroethane (HFC-152a); 1,1,1,3,3-pentafluoropropane (HFC-245fa);1,3,3,3-tetrafluoropropene (HFO-1234ze); 1,1,1,4,4,4-hexafluorobut-2-ene(HFO-1336mzzm); butane; isobutane; normal pentane; isopentane;cyclopentane, and combinations thereof.
 6. The poured-in placepolyurethane foam of claim 1 where said cells contain a gas comprisingHFCO-1233zd(E) and cyclopentane.
 7. The poured-in place polyurethanefoam of claim 6 wherein trans-1-chloro-3,3,3-trifluoropropene(HFCO-1233zd(E)) is provided an amount of from about 5 wt. % to about 99wt. % and cyclopentane is provided in an amount from about 95 wt. % toabout 1 wt. %.
 8. The poured-in place polyurethane foam of claim 6wherein trans-1-chloro-3,3,3-trifluoropropene (HFCO-1233zd(E)) isprovided an amount of from about 25 wt. % to about 90 wt. % andcyclopentane is provided in an amount from about 75 wt. % to about 10wt. %.
 9. The poured-in place polyurethane foam of claim 6 whereintrans-1-chloro-3,3,3-trifluoropropene (HFCO-1233zd(E)) is provided anamount of from about 50 wt. % to about 85 wt. % and cyclopentane isprovided in an amount from about 50 wt. % to about 15 wt. %.
 10. Thepoured-in place polyurethane foam of claim 1 having a free rise densityof 1.87 lb/ft³.
 11. The poured-in place polyurethane foam of claim 1having a core density of 2.21 lb/ft³.
 12. The poured-in placepolyurethane foam of claim 6 having a free rise density of greater than1.71 lb/ft³.
 13. The poured-in place polyurethane foam of claim 6 havinga core density of greater than 2.33 lb/ft³.
 14. A pour-in place foampremix comprising a polyol; a blowing agent comprisingtrans-1-chloro-3,3,3-trifluoropropene (HFCO-1233zd(E)); at least onesurfactant; and at least one catalyst.
 15. The pour-in place foam premixof claim 14 wherein the blowing agent further comprises one or moreadditional blowing agents selected from the group consisting of water,organic acids that produce CO₂ and/or CO, hydrocarbons; ethers,halogenated ethers; esters, alcohols, aldehydes, ketones,pentafluorobutane; pentafluoropropane; hexafluoropropane;heptafluoropropane; trans-1,2 dichloroethylene; methylal, methylformate; 1-chloro-1,2,2,2-tetrafluoroethane (HCFC-124);1,1-dichloro-1-fluoroethane (HCFC-141b); 1,1,1,2-tetrafluoroethane(HFC-134a); 1,1,2,2-tetrafluoroethane (HFC-134); 1-chloro1,1-difluoroethane (HCFC-142b); 1,1,1,3,3-pentafluorobutane(HFC-365mfc); 1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea);trichlorofluoromethane (CFC-11); dichlorodifluoromethane (CFC-12);dichlorofluoromethane (HCFC-22); 1,1,1,3,3,3-hexafluoropropane(HFC-236fa); 1,1,1,2,3,3-hexafluoropropane (HFC-236e);1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea), difluoromethane (HFC-32);1,1-difluoroethane (HFC-152a); 1,1,1,3,3-pentafluoropropane (HFC-245fa);1,3,3,3-tetrafluoropropene (HFO-1234ze); 1,1,1,4,4,4-hexafluorobut-2-ene(HFO-1336mzzm); butane; isobutane; normal pentane; isopentane;cyclopentane, and combinations thereof.
 16. The pour-in place foampremix of claim 14 wherein the blowing agent further comprisescyclopentane.
 17. The pour-in place foam premix of claim 14 wherein thefoam premix has a foam reactivity gel time of about 55 seconds.
 18. Thepour-in place foam premix of claim 14 wherein the foam premix has a foamreactivity tack free time of about 100 seconds.
 19. The pour-in placefoam premix of claim 16 wherein the foam premix has a foam reactivitygel time from 52 to 55 seconds.
 20. The pour-in place foam premix ofclaim 16 wherein the foam premix has a foam reactivity tack free timefrom 85 to 100 seconds.